Interpolymers of a 2-alkenyl 2-alkenoate, a 2-alkenyl alcohol, and another copolymerizable monoolefinic compounds



Patented May 27, 1952 INTERPOLYMERS OF A 2-ALKENYL 2-AL- KENOATE, AZ-ALKENYL ALCOHOL, AND ANOTHER COPOLYMERIZABLE MONOOLE- FINIC COMPOUNDPliny 0. Tawney, Passaic, N. J assignor to United States Rubber Company,New York, N. Y., a corporation of New Jersey No Drawing. ApplicationOctober 23, 1948, Serial No. 56,259

15 Claims. (01. 260-78. 5)

My invention relates to a new class of soluble,

unsaturated, ternary interpolymers of a 2-alkenyl 2-a1kenoate, a2-alkenyl alcohol, and a different copolymerizable monoolefinic compoundof a certain class, which interpolymers can be converted to a solventanda heat-resistant state by further polymerization or copolymerization, aswell as to a method of preparing these interpolymers.

The copolymers of 2-alkenyl 2-alkenoates such as allyl acrylate withvarious copolymerizable monoolefinic compounds such as methyl acrylateor diethyl fumarate are highly regarded by the art because of theiroptical clarity and resistance to discoloration upon aging, even atelevated temperatures. However, the preparation of such copolymers isattended by gelation of the reaction mixture before more than minoramounts of the monomeric starting materials have been converted to thecopolymeric form. The resulting mixtures of insoluble gel, low molecularweight copolymers and unreacted monomers are not only difficult tomanipulate but are actually of little or no commercial utility sincemany processes such as coating and molding require a uniform andinitially soluble, fusible resin which, after application on'shaping,can be subsequently cured or polymerized to a solvent and heat-resistantstate. Soluble, unsaturated copolymers of 2-alkenyl 2-alkenoates andcopolymerizable monoolefinic compounds can be obtained in very lowyields by halting the copolymerizations before gelation occurs. However,the resulting copolymers must be submitted to extensive purificationoperations to I; remove the large amounts of unreacted starting ableproperties of the resulting resin be retained.

I have now discovered a method whereby the prior art difficulties areovercome, which comprises interpolymerizing a mixture of a 2-alkenyl2-alkenoate and a copolymerizable monoolefinic compound of a certainclass with a 2- alkenyl alcohol to form valuable new interpolymers. Bymy method the major proportion of both the 2-alkenyl 2-alkenoate and thecopolymerizable monoolefinic compound can be converted to novel, solubleinterpolymeric bodies without danger of gelation. Unlike the prior art,my reaction proceeds readily at moderate temperatures and requires nospecial precautions such as have heretofore been employed in attempts toavert or delay gelation.

The interpolymerizable 2-alkenyl alcohols which are useful in myinvention are of the type formula R*CH=CR*CH2OH where one R" is hydrogenand the other R* is one of the radicals hydrogen, chlorine, methyl,ethyl and phenyl. Exemplary of such alcohols are allyl, methallyl,2-chloroallyl, ethallyl, crotyl and cinnamyl alcohols, among which thosecontaining a terminal methylene group, e. g., allyl alcohol, arepreferred. I have found that the presence of as little as 0.2 mole ofthe interpolymerizable 2-alkeny1 alcohol (per mole of the 2-alkenylalkenoate) in the polymerizing reactant mixture is sufiicient to securea marked increase in the conversion of the 2-alkenyl alkenoate and theother copolymerizable monoolefinic compound to the solubleinterpolymeric form. The major proportion of the latter compounds can beconverted to soluble interpolymers when about 3-5 moles of a 2-alkenylalcohol per mole of 2-alkenyl alkenoate are initially present, and evenhigher conversion can be obtained as the proportion of the alcohol isfurther increased, e. g., to 7-10 moles.

Suitable 2-alkenyl 2-alkenoates are those having the type formulawherein one R* and one R are hydrogen while the other R* and R" arehydrogen, chlorine, methyl or phenyl. Illustrative of such compounds areallyl acrylate, allyl methacrylate, methallyl acrylate, allylchloroacrylate, allyl crotonate, cinnamyl acrylate, allyl cinnamate andchloroallyl chloroacrylate. pounds in which the terminal R.* and R arehydrogen, as in allyl acrylate, are preferred since they are polymerizemost readily and rapidly at moderate temperatures to yield solubleinterpolymers capable of being readily cured to an insoluble, infusiblestate.

The copolymerizable monoolefinic compounds which are operable in myinvention are the solely aliphatic monoolefinic compounds represented bythe type formula RR'C=CRR" wherein R is hydrogen, fluorine or methyl; R.is hydrogen,

fluorine, carboxyl or a group hydrolyzable, to carboxyl, includingcarbalkoxy (e. g., carbomcthoxy, carboethoxy, carbohexoxy), carbamyl,N-alkylcarbamyl (e. g., N-methyl-carbamyl), and car- T hOSecombonitrilo; R ishydrogen, lower alkyl (e. g.,

methyl ethyl),v chlorine, fluorine, carboxyl or a group hydrolyzable tocarboxyl as defined above;

R." is chlorine, fluorine, carboxyl, a group hydrolyzable to carboxyl,alkoxy (e. g., methoxy,

ethoxy, propoxy, isopropoxy, butoxy, .amyloxy, hexoxy, heptoxy, octoxy,nonoxy,udecoxy), acyloxy devoid of olefinic and acetylenic unsaturation,i. e., alkanoyloxy (e. g., acetoxy, propionoxy, butyroxy) acyl devoid ofolefinic and acetylenic unsaturation, i. e., alkanoyl, (e.- g.,- acetyl,propionyl, isobutyryl); or, R' may be car-boxymethyl, when R," iscarboxyl or a group hydrolyzable thereto; or R' may together with Rcomprise a carbanhydro group -COO-CO or a carbimido group -CONR+CO,where R+ is hydrogen, or alkyl (e. g., methyl, ethyl, -propyl,-isopropy1, butyl, isobutyl, ,amyl, cyclo pentyl, hexyl, cyclohexyl,heptyl, octyl, nonyl, decyl).

Bytheappropriatechoice from the above class of copoly-merizablemonoolefinic compounds, nu- -merousvariations inithe properties of theresulting soluble, unsaturated ternary inter-polymers can be attained.

"-Thus, copolymer-izationwith a halogenated linonoolefinic compoundsuch: as .vinyl chloride or vinylidene chloride as the thirdcomponentyields -polymeric materials of increased flame-resistance -*andoften of greatenhardness. Harder products -.can also be obtained by thecopolymerization with olefin-ici acid, nitriles, amides and imides, e.g., acrylonitrile .-or ,methacrylamide, as the third component. Ontheother hand,--softer and more flexible products. can usuallybe obtainedbythe copolymerization with, aszthe third component, .o'neofzthe-aolefinic-acid esters of; nonenic monohydricaalcohols; includingthe --alkyl acrylates,

-tmethacrylates, maleates, fumarates, itaoonates,

-.- mesacona.tes, ,and aconi t ates, particularly such -cesters.zderived rom alcohols. containing a chain ,ofttwoxorrmore carbon atomsea-g ethanol, n- :butanol, 2,vethyl- -l-hexanol andl-octanol.

1Thenon-hydrocarbon monoolefinic' compounds .used 2 in: the process ,ofthis invention result in products which can:- be, used. to' producemolded ance tolattackby hydrocarbon sol-vents;

Of the wide variety of such copolymerizable monoolefiniccompoundswhich-Imay use in my invention, 1 especially prefer, to employthe following because of the superior properties of thefDIQdlllCtSyfiRd-bGCQMSB of-the easeandconven- "ience with which thecopolymerizationcan be carriedout, as -well-as-for reasons of cconomy,

etc:

lfi'Ihe acrylic esters-of the-saturated aliphatic monohydric alcohols,such as -'methyl 7 acrylate,

methyl -methacrylate,-butyl acrylate; butyl methethenvinyl hexyl ether,.etc.

4. The esters ofcalphaeolefinic,polyoarbcxylic acids with saturatedaliphaticgmonohydric al- -cohols, such as diethyl .fumarate, .bis (beta--chloroethyl) fumarate, dibutyl. fumarate; bis (2- .ethylhexyl)iumarate, .dimethyl itaconate, .di- "ethyl itaconate, dihexyl.itaconate, dicyclohexyl articles or cured. surface-coatings havingcertain desirable-properties; notably; exceptional resistacids.

:itaconate, .dioctyl itaconate, -;;b is( -beta-ch1orocompoundsareacrylamide, N-methylacrylamide, 7acrylonitrile, methacrylonitrile,

fumaronitrile, maleimide, N-butyl maleimide, vinyl chloride,

.vinylidene chloride, methyl vinyl ketone, etc.

;In--carry-ing out my invention, the Z-alkenyl 2- alkenoate is heated,e. g., at (SO-120 C., with from 0.1 to 8.0, preferably from 0.5 to 6.03and particularly from 0.5 to about 4.0 molar equivalents of thecopolymerizable aliphatic, non-hydrocarbon monoolefinic compound ormixture of such compounds andwith from 0.2 to 12, preferably 0.2-9.0;molar equivalents of a2-alkenyl alcohol.

:The reaction time will varyto some extent depending upon theinterpolymerizable reactants .-employed and upon the relativeproportions thereof; timesinthe range oiirom l to ,100

hours are usuallysu-fiicient, although. longer times, e. g.,-20O-300hours, may be employed where very high yieldsofthe soluble interpolymersare desired. My interpolymerization reployed in amounts of from 0.1to,10%, us ually ir0m=0,15%, by weight of the. reactant mixture, and,may be added either atthe beginning. or incrementallythroughoutthecourseof the re- ;action. Thecourse of thereaction can beiollowed byobserving theincrease. in viscosity. of the reaction mixture, and theproductcanbe isolated therefromby removal of unreactedstarting materialsby preferential extraction, evaporationorrdistillation. Although it isunnecessary for most commercial applications, the. interpoly- -mers-canbe further purified, if necessary, e., g.,

f er-analytical purposeabysolution in ,a minimum volume of a solventsuch. as acetone andprecipitation by dilution with n-hexane.

- {The :soluble interpolymeric products .thus obvalues of from about 50to 225. The amount of this residual unsaturation in my interpolymersivaries with the monomeric. reactants em- ;ployedand,; moresignificantly, with the relative .proportions thereof within theconcentration .ranges previously cited. For -most' a plications '1 12have found. that my, interpolymers having: io-

dine values of from about to about 1-80 are completely satisfactory. Anespecially preferred class of products having :an iodine vnurr iber ofabout .80 to :are those devised from the acrylic, esters V of thesaturated aliphatic mono- My, new interpolymers can be employed. as

: thermosetting molding powders and in such aplplications they can bereadily formed into .var- "iousshapes,,-,e. ,g., rods and :sheets, whichare notable for their high degree of optical ,transparency and freedomfrom brittleness. My

. interpolymers can likewise ,be employed, in the presence of diluents,for coating, impregnating assess re frDeated1y througha-180'anglefiwithnoevidence reveals a low orderof strain. It possesses aBarcolhardness of 4-7, and Rockwell hardnesses of M99 and P82;

late-19:2 parts of nbuty1-acrylat'e and 525.6 parts of methallyl alcoholis heated with 4.01 parts of benzoyl' peroxide for 24 hoursat 113 C. Theexcess methallyl alcohol isthen removed "by distillation under reducedpre'ssure'and the interpolymer is'purified by repeatedsolution inacetone and precipitation with n-hexane' After drying in vacuo, 151parts of polymeric solid are obtained; Iodine number 102.1; [1 1 0.084;

Sevenpartsof the above ternary interpolymer A mixture of 56.1 parts-of'allyl acryla-te, 64.1 parts of n-butyl acrylate; 480.8 parts ofmethallyl alcohol and 3.72 parts of benzoyl peroxide is heated for '24hours at 112 C. After isolating andpurifying the-interpolymer as inExample .2, 95:3'parts. of solid product were obtained. Iodinenumber'82'.8j 1 0.74:

Four'parts of the'interpoly-mer aredissolved in a m'ixture of 7 partsof'acetone, 2.4 parts of xylene;'0.4 part of cyclohexanone and 0.2 part of2-ethylhexanol-lp The solution 'wasflowed ontoa glass panel and bakedfor minutes at 200 C. to yield a tack-free film which iscolorless;man-resistant and insoluble in organic solvents.

EXAMPLE 5 Fifty-six-and onetenth parts of allyl acrylate and 86.1 partsof methyl acrylate are dissolved in 568.8. parts-of methallyl- -alcoholtogether with 2.275 parts of benzoyl peroxide. The resulting solution isheated for 24 hours at 107 C. and-the product is isolated and purifiedas in previous'ex-' amples to yield "133' parts "of solidinterp'olyirie'ru Iodine number 891;: [1,1 0.078. Asolution'of '5 partsof the interpolymer: in 5 parts of cyclehexanonehas a-viscosity of=poises'at 25C.

A solution of 8 parts of the interpolymer -dis-; solved in'a mixture of14 parts of acetone', -'4l8 parts of xylene; 0.8 part ofcyclohexanone'jand 0.4 part of 2-ethylhe'xanol 1is fio'wed onto a glasspanel and baked for 20 mir1utes at200CL The resulting smooth, adherent'filfdh'al's "g'o'od'mar resistance and is not attacked by organicsolvents.

into a shallow ferro=chrome mold all-y benzoyl peroxide Io de i i iiiilie I Four-parts-of the-interpolymer redissolve benz oyl presie-"rolehours" g M tsorpure' interp 1merare obtaine tron" product.-Iodine number was;

. v. 3 h1 wer inertfto brganicsolventsf he is as e eanic iqr ess e enew. ai ddi'tibri'al Heating hddhad no I ui'tariziusefiaf A solutioncomprising 112.2 parts of-allylfac'ry- 20 EXAMPLE '7 .Aninterpolymen-obtained -i-r'r-"the of 49i'l -parts-byheating a mixture of33.6; parts; of 'ac'rylate; 3.85 3 parts ofn -butyl-;: acrylat'e, 149 .6partskof- -me t-hall;yl-* alcohol and ;.1;.;l6 par-ts of-w'benzoylperoxide for 20.5 hours at -'1- 1 1-- Q. is treated i'n-the same manner;as;-the interpolyn er ofeExa-mpl- "5; but-"-yields-a;;film which is sexnewhavless flexibledue to -the smaller amount of n 'butyl acrylate in"the inter-polymer. 7

EXAMPLE 8 By heating "a solutiorf of' '44.9 parts "of: *allyl acrylate,51.3 parts-'of-nebutyl acrylate and 2.33

partsof benzoyl peroxide in 288 Qparts of methallyl alcohol" for2hour's-at interpolyxner membran s comparable -to those press 9- Asolution of 's'sli' parts of 511371 wh n: 15.0

v unsaved iii-28414"paitsiof allyl alcohol is heated fo 'z'laliours'afij96*0. ter isolating; and purify the usual: fashion. :6

din a mixtureof pa'rts of xyleneizfi; parts of cyclghexanone and- 0.5part: pf -carbitof'dtlte. The;so lution i s flowedonto a glass "pa V,fid balred at 200* C: for- 2 0- minutes.- The :fil m thus formed isclear, colorless, smooth, glossy and indifferent to the action oforganic solvents. When scraped with a sharp knife the film separatesfrom-the--glass-incontinuous flexible ribbons.

EXAMPLE 10'" Thirty-t-hree andfour-tenths parts of allyl methacrylateand-10.2 parts of isobutyl acrylate are dissolve-din 1174.4 parts ofallyl alcoholtogather with 1.9'Tparts of ben'zoylperoxide and theresulting: solutionflis heated for 24 hours -at 97 C. Forty-two ahdfive-tenthspersonnte'rpolymer areiisc'ilated ffrom thef reaction mixtureby the' methodof previous examples. Iodine number 120.2.

and laminating operations, and for such purposes, the crudeinterpolymerization reaction mixtures can themselves be used if they arefirst diluted with a suitable high boiling solvent, e. g.,

From Table I above it is readily apparent that the presence of evensmall amounts of an interpolymerizable 2-alkenyl alcohol eifects a.significant increase in the amounts of the 2-alkenyl 2aly and su s qu yat d to remov a 5 kenoate and the copolymerizable monoolefinic unreacted2-a1keny1 aICOlIO In Dp compound converted to the soluble copolymerictmnsmy mterpolymers Yleld clear, fiexlbk films rm, and that thisconversion can be increased to whose lack color r ers t en pa cu arly amarked extent by increasing the amount of the sultable r yeing and lf eta 2-alkenyl alcohol in the reactant mixture. The y pfl y l can 11k6W1Sebe dissolved 111 vastly superior efiectiveness of my interpolymerqmcopolyme e et y c co izable 2-alkenyl alcohols in comparison with thetolyl fl y fi. f y f Styrene, non-polymerizable solvents employed in theart is or vinyl butyrate, to meld solutions which are likewise mteworthycapable of being totally polymerized, leavlng no solvtent;1 to beefvaporatedthsuch solutions alie 15 EXAMPLE 2 ar ic arl use u where eremoval 0 a so s fromya coating or impregnating composi A mixture of112.2 parts of allyl acrylate, 38.5 tion would constitute a technicalhazard. They parts of t acrylate and 452 Parts of meth" are likewiseuseful as initially fluid molding comanyl .heated mgether with Partspositions which can be cured with a minimum of of bepzoyl P q for hoursat The shrinkage reaction mlxture is then cooled and, after the ad- Uponheating 8. at compositions dltlon of a traceof hydroquinone to repressfurcontaining my interpolymers, particularly in the ther merlzatlon tumjeacted i l f alpresence of added catalyst, further polymerizacohol 1sremoved by dlstlnatm} under dmtlmshed tion is induced and the resultingproducts dis- 25 pressure h R W F resldue is punfied by play dimensionalstability even at elevated temt fi t dlssolvmg 1t m acetone P peraturesas well as a high degree of resistance with i A final Preclpltatlon toattack by solvents. Suitable inert addends camid out by adding methanolto an acetate including dyes, pigments, fillers and plasticizers ofmterpolymer and F 18 can be incorporated with my interpolymers pref- 5gg vacluo N welght yleldmg erably at the soluble, fusible stage prior tofinal 5 0 2 m t f 9 m number aura (WlJs) 98.6; (intrinsic viscosity inacetone) The following examples disclose my invention 0095' in detailAll parts are by weight The lodme number lndlcates the large amount ofunsaturatlon in the interpolymer which is EXAMPLE 1 available forfurther polymerization.

Various mixtures of a 2-alkenyl 2-alkenoate, F (a) A 5911117100 0 5Parts Of the p ly e a Z-alkenyl alcohol and another copolymerizablealssfllved m a mlxtule 0f 4 Parts of acetone, mon l fi j Compound areheated at Q in part of cyclohexanone and 0.5 part of toluene thepresence of benzoyl peroxide as a promoter lspoured Onto a glass paneland baked for 20 until in each case t point of incipient ge1a.. 40mlnutes at 200 C. The resultant film lS smooth, tion is attained. Thereaction mixture is then glossy, mar-resistant, and is tack-free evenwhen diluted with n-hexane and the precipitated int It s not discoloreddurin e C re and is terpolymer is further purified by solution in alnert t0 the actlon 0f Orgamc Solventsminimum volume of acetone andreprecipitation (b) Seventeen and four-tenth P s Of th with n-hexane.The products a finally i d lnterpolymer together with 0.087 part ofmalelc in vacuo to constant weight, anhydride are dissolved in a mixtureof 17.5 parts In Table I below are summarized the amounts of Xylene,Parts Of acetflne, p of of the starting materials, the peroxide and themethyl ethyl ketone, 2 Parts Of y o xa o polymeric products as well asthe reaction times. d P Of y 0 e resulting To emphasize the advantagesof my invention solution is flowed onto a, metal plate and bakedexamples of the prior art copolymerization of at 200 C. for 20 minutes.The result film 1S 2-alkenyl 2-alkenoates and copolymerizable sm o h. loy. c l m r-r si t n and unmonoolefinic compounds in the absence ofaffected by organic solvents. The adherence of 2-alkenyl alcohols areincluded (L1, 5, 8, 10, 12, the film to metal is excellent, and thecoated 13, 14, 15). plates can be hammered, twisted, bent or flexed ITable I e Reaction Alkellyl Allzenoate Copolymcrizable Monomer fi igfg$522K: gggg 1 Allyl Acrylate 100 Dlethyl Fumarate... 50 0.00 5.75 7. 2.do do 50 0.8 1.9 14.1 1.0 1.7 20.3 4 do 1.2 2.0 44.0 50 (BenzylAlcohol) 1.6 1.5 18.6 Allyl Alcohol l. 7 4. 5 74. 6 "Mao... .-do 5.011.75 158.0

Diethyl Maleate 0.5 1.7 4.05 do 50 1.0 2.9 27.0 Dimethyl Itaconate 0. 026. 0 4.1 .do 20 Allyl Alcohol 100 0.8 1.9 41.0 do 20 (BenzylAlcohol)100 0.8 5.9 10.3 do 20 (Carbon Tetra- 100 0.8 5.9 3.48

Chloride). do 20 (Benzene). 0.8 3.9 14.5 Butyl Vinyl Ether. 200 1.5 0.29.6 do 200 4.2 240.0 142.0

1 No evidence of incipient gelation.

2-ethylhexanol-1, and the solution is flowed onto a glass panel. Afterbaking for 20 minutes at 200 C. a smooth, glossy, adherent film isformed which displays good mar resistance and is not attacked by organicsolvents.

Having thus described my invention, what I claim and desire to protectby Letters Patent is:

1. A soluble, ethylenically unsaturated, ternary interpolymer ofmonomers consisting of (A) a 2-alkenyl Z-alkenoate, (B) acopolymerizable monoolefinic compound selected from the group consistingof acrylic esters of the saturated aliphatic monohydric alcohols, vinylesters of the saturated aliphatic monocarboxylic acids, vinyl alkylethers, vinyl methyl ketone, esters of alphaolefinic polycarboxylicacids with saturated aliphatic monohydric alcohols, acrylamide,N-methylacrylamide, acrylonitrile, methacrylonitrile, fumaronitrile,maleimide, N-butyl maleimide, vinyl chloride, and vinylidene chlorideand (C) a 2-alkenyl alcohol, the said interpolymer being derived from aninterpolymerizable mix containing from 0.2 to 12 molar equivalents of(C) and from 0.1 1508.0 molar equivalents of (B) per molar equivalent of(A).

2. A soluble ethylenically unsaturated ternary interpolymer as in claim1 having a Wijs iodine number from 80 to 180.

3. A soluble ethylenically unsaturated ternary interpolymer as in claim1 in which the 2-alkenyl alcohol (C) is allyl alcohol.

4. A soluble ethylenically unsaturated ternary interpolymer as in claim1 in which the copolymerizable monoolefinic compound (13) is an acrylicester of a saturated aliphatic monohydric alcohol.

5. A soluble ethylenically unsaturated ternary interpolymer as in claim'1 having a Wijs iodine number of from 80 to 180, in which thecopolymerizable monoolefinic compound (B) is an acrylic ester of asaturated aliphatic monohydric alcohol.

6. A soluble ethylenically unsaturated ternary interpolymer as in claim1 in which the copolymerizable monoolefinic compound (B) is a vinylester of a saturated aliphatic monocarboxylic acid.

7. A soluble ethylenically unsaturated ternary interpolymer as in claim1 in which the copolymerizable monoolefinic compound (B) is analpha-olefinic polycarboxylic acid ester of a sat urated aliphaticmonohydric alcohol.

8. A soluble ethylenically unsaturated ternary interpolymer as in claim1 in which the 2-alkenyl alkenoate (A) is allyl acrylate.

9. The method of preparing a soluble ethylenically unsaturatedinterpolymer of (A) a 2-alkenyl 2-alkenoate, (B) a copolymerizablemonoolefinic compound selected from the group consisting of acrylicesters of the saturated aliphatic monohydric alcohols, vinyl esters ofthe saturated aliphatic monocarboxylic acids, vinyl alkyl ethers, vinylmethyl ketone, esters of alpha-olefinic polycarboxylic acids withsaturated aliphatic monohydric alcohols, acrylamide, N-methylacrylamide,acrylonitrile, methacrylonitrile, fumaronitrile, maleimide, N-butylmaleimide, vinyl chloride and vinylidene chloride, which comprisescarrying out the interpolymerization in the presence of (C) a 2-alkenylalcohol, from 0.2 to 12 molar equivalents of (C) and from 0.1 to 8.0molar equivalents of (B) being present per molar equivalent of (A).

10. The method as in claim 9 in which the 2-alkenyl alcohol (C) is allylalcohol.

11. The method as in claim 9 in which the copolymerizable monoolefiniccompound (B) is an acrylic ester of a non-olefinic aliphatic monohydricalcohol.

12. The method as in claim 9 in which the copolymerizable monoolefiniccompound (B) is a vinyl ester of a non-olefinic aliphatic monocarboxylicacid.

13. A soluble ethylenically unsaturated tenary interpolymer of monomersconsisting of allyl acrylate, a lower alkyl acrylate and allyl alcoholhaving a Wijs iodine number of about to the said interpolymer beingderived from an interpolymerizable mix containing from 0.2 to 12 molarequivalents of allyl alcohol and from 0.1 to 8.0 molar equivalents oflower alkyl acrylate per molar equivalent of allyl acrylate.

14. A soluble ethylenically unsaturated ternary interpolymer of monomersconsisting of allyl acrylate, diethyl fumarate and allyl alcohol thesaid interpolymer being derived from an interpolymerizable mixcontaining from 0.2 to 12 molar equivalents of allyl alcohol and from0.1 to 8.0 molar equivalents of diethyl fumarate per molar equivalent ofallyl acrylate.

15. A soluble ethylenically unsaturated ternary interpolymer of monomersconsisting of allyl acrylate, vinyl acetate and allyl alcohol the saidinterpolymer being derived from a polymerizable mix containing from 0.2to 12 molar equivalents of allyl alcohol and from 0.1 to 8.0 molarequivalents of vinyl acetate per molar equivalent of allyl acrylate.

PLINY O. TAWNEY.

REFERENCES CITED I The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number

1. A SOLUBLE, ETHYLENICALLY UNSATURATED, TERNARY INTERPOLYMER OFMONOMERS CONSISTING OF (A) A 2-ALKENYL 2-ALKENOATE, (B) ACOPOLYMERIZABLE MONOOLEFINIC COMPOUND SELECTED FROM THE GROUP CONSISTINGOF ACRYLIC ESTERS OF THE SATURATED ALIPHATIC MONOHYDRIC ALCOHOLS, VINYLESTERS OF THE SATURATED ALIPHATIC MONOCARBOXYLIC ACIDS, VINYL ALKYLEHTERS, VINYL METHYL KETONE, ESTERS OF ALPHAOLEFINIC POLYCARBOXYLICACIDS WITH SATURATED ALIPHATIC MONOHYDRIC ALCOHOLS, ACRYLAMIDE,N-METHYLACRYLAMIDE, ACRYLONITRILE, METHACRYLONITRILE, FUMARONITRILE,MALEIMIDE, N-BUTYL MALEIMIDE, VINYL CHLORIDE, AND VINYLIDENE CHLORIDEAND (C) A 2 ALKENYL ALCOHOL, THE SAID INTERPOLYMER BEING DERIVED FROM ANINTERPOLYMERIZABLE MIX CONTAINING FROM 0.2 TO 12 MOLAR EQUIVALENTS OF(C) AND FROM 0.1 TO 8.0 MOLAR EQUIVALENTS OF (B) PER MOLAR EQUIVALENT OF(A).